In-situ investigation of solid-electrolyte interphase formation on the anode of Li-ion batteries with Atomic Force Microscopy

Wang, Lixin; Deng, Da; Lev, Leonid; Ng, S.F.

doi:10.1016/j.jpowsour.2014.04.113

Cited by 42 publications

(28 citation statements)

References 14 publications

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“…This implies that the viscoelasticity of the SEI film withoutL i 2 SO 4 treatment is poor. [21] As reported, the formation of cracks in the surface of SEI would lead to further sustained reductions.A lthough occurring only on as mall scale, the breakdown and repair of SEI film will thicken the SEI, and hence waste Li + ions and increasei nterfacei mpedance. [22] This should be the reason for the bad cycle performance and capacity fading.…”

Section: Graphiteelectrode Surface Characterization By Scanning Electmentioning

confidence: 74%

Pretreatment of Graphite Anodes with Lithium Sulfate to Improve the Cycle Performance of Lithium‐Ion Batteries

Cui

Tang

et al. 2016

Energy Tech

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Graphite electrode surfaces are pretreated by spray‐deposition method with 0.5 mol L−1 Li2SO4 aqueous solution. The physical and electrochemical properties of a solid electrolyte interphase (SEI) film formed on the surface of Li2SO4‐treated graphite electrode are investigated by Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, and electrochemical measurements. The results show that the SEI film formed, promoted by Li2SO4, is thin, stable, effective, and elastic to accommodate volume changes of graphite electrode during electrochemical cycles. Due to the fact that the Li/mesophase carbon microbeads (MCMB) cell based on Li2SO4‐treated graphite electrode exhibits excellent cycling performance and low interfacial impedance, we can deduce that such modifies have positive implications for lithium‐ion batteries (LIBs), offering the possibility of faster‐charging LIBs and LIBs that are suitable for rate‐demanding applications, such electric vehicles and hybrid electric vehicles.

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Section: Graphiteelectrode Surface Characterization By Scanning Electmentioning

confidence: 74%

Pretreatment of Graphite Anodes with Lithium Sulfate to Improve the Cycle Performance of Lithium‐Ion Batteries

Cui

Tang

et al. 2016

Energy Tech

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“…Other studies have also employed in situ AFM on battery electrodes . This includes several that look at SEI formation on anodes . PeakForce tapping AFM was also recently used to examine near surface mechanical properties .…”

Section: Introductionmentioning

confidence: 99%

Control and Optimization of the Electrochemical and Mechanical Properties of the Solid Electrolyte Interphase on Silicon Electrodes in Lithium Ion Batteries

Tokranov

Kumar

et al. 2016

Advanced Energy Materials

104

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here signifi cant research is focused on higher voltage electrolytes). [ 2,3 ] The thicker anode SEI fi lms make a much larger contribution to irreversible Li consumption. However, there is very little understanding of how the chemomechanical degradation of SEI leads to capacity loss.Full battery models have employed descriptions of long-term Li capacity loss due to SEI, [ 4,5 ] some of which include specifi c models for the growth of the SEI layer. [ 6,7 ] SEI stability is particularly important with newer anode materials such as silicon and tin, which have much higher capacity than the intercalation materials which are currently used commercially. For example, the capacity increase of silicon is almost ten times that of graphite. However, this is accompanied by a large volume change (>300%), which leads to mechanical degradation of the SEI layer during repeated expansion and contraction of the electrode. Mechanical degradation of silicon electrodes has been addressed in recent research, [ 8,9 ] including work on damage mechanisms such as critical fracture size, [ 10 ] impact of the surface oxide, [ 11 ] other mechanical properties, [ 12 ] and some scalable mitigation techniques. [ 13 ] Experimental investigations of SEI degradation are signifi cantly more challenging, because the layers are very thin and they typically consist of multiple phases. Some of the relevant issues have been addressed in recent experiments, [14][15][16][17][18] but there is still only very limited information about SEI formation and its mechanical degradation on silicon.The research reported here employs several different techniques to probe critical SEI properties, with a focus on in situ electrochemical atomic force microscopy (AFM). Other studies have also employed in situ AFM on battery electrodes. [19][20][21][22] This includes several that look at SEI formation on anodes. [23][24][25][26] PeakForce tapping AFM was also recently used to examine near surface mechanical properties. [ 27 ] Our investigations are primarily based on comparisons between "slow cycling" and faster "pulse cycling." This includes detailed analysis of in situ AFM data, supported with electrochemical impedance spectroscopy (EIS). A structural model that explains the observed mechanical and electrochemical properties is proposed. Based on this description, a simple mathematical model is then developed The formation of the solid electrolyte interphase (SEI) on Si is examined in detail using several in situ techniques. The results show that employing different conditions during the fi rst lithiation cycle produces SEI fi lms with substantially different properties. Longer time at higher potentials produces softer SEI, whereas inorganic phases produced at lower potentials have higher elastic moduli. The SEI thickness stabilizes during the fi rst cycle; however, the SEI resistance decreases during the fi rst 20 cycles (in sharp contrast to typical surface passivation processes, where resistance is expected to increase with time). This behavior is consistent with t...

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“…Both steps, i.e., the initial reversible and the later irreversible SEI formation can be observed in an in operando STM experiment. Studying the SEI film by STM, however, is limited by the poor electronic conductivity of the SEI compounds . The mechanical interaction of an AFM cantilever is not disrupted by the electronic properties of the SEI film and hence AFM may be a better tool to study the SEI.…”

Section: Energy Conversion Beyond Catalysis: Batteriesmentioning

confidence: 96%

Electrochemical Scanning Probe Microscopies in Electrocatalysis

et al. 2018

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surface coordination, strain effects, [6][7][8][9] ligand effects, [10,11] ensemble effects, [12] and the electrolyte composition. [13] A detailed understanding of these effects requires experimental and computational procedures to investigate the working mechanisms of the electrocatalysis. Ideally, atomically resolved topographic and chemical information of the catalyst surface under reaction conditions is required. Transmission electron microscopy (TEM) has been reported to be capable of in operando investigation of catalyst structures while catalytic reactions are taking place. [14] However, the instrumentation utilized for such purpose has very strong restrictions and realistic operating conditions cannot be easily applied so far. Alternatively, scanning probe microscopies (SPMs) and electrochemical scanning probe microscopies (EC-SPMs) are able to perform structural measurements of catalytic systems under reaction conditions with resolution down to atomic scales. Normally, EC-SPMs, for instance electrochemical scanning tunneling microscopy (EC-STM), electrochemical atomic force microscopy (EC-AFM), and scanning electrochemical potential microscopy (SECPM), can provide structural information on the solid side of the electrode/electrolyte interface at the atomic level for conductive samples (EC-STM is limited in the case of semi/nonconductive samples). However, these techniques usually lack the capability of chemical sensitivity, ultrahigh resolution reactivity monitoring, and probing the property of the electrolyte side of the interface. One well-developed exception is the scanning electrochemical microscopy (SECM), which will also be discussed in detail within this review. Additionally, SECM and related methods permit gleaning information about the electrolyte side of the electrochemical interface. However, the resolution of SECM and related methods is limited by the size of the SECM-probe and the working principle of SECM.In this review, first a very brief overview on electrocatalysis and on the importance of model substrates for understanding the fundamental underlying principles is given. Thereafter, the operational principle of different SPM techniques is summarized. The main focus of the work lies then on the application of the techniques to study phenomena important for electrocatalysis, including surface topography and adsorption processes. Within that context, also the application of room Improvements toward highly efficient electrochemical energy conversion require a detailed understanding of the underlying electrochemical processes at electrified solid-liquid interfaces. In situ and in operando studies by means of electrochemical scanning probe microscopy (EC-SPM) have become indispensable experimental tools due to their capability of resolving surface topography down to the atomic level even within the harsh environment of electrolytes. EC-SPM methodologies have thus contributed tremendously to the current understanding of electrocatalysis. In this review article, recent achievements in complement...

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In-situ investigation of solid-electrolyte interphase formation on the anode of Li-ion batteries with Atomic Force Microscopy

Cited by 42 publications

References 14 publications

Pretreatment of Graphite Anodes with Lithium Sulfate to Improve the Cycle Performance of Lithium‐Ion Batteries

Pretreatment of Graphite Anodes with Lithium Sulfate to Improve the Cycle Performance of Lithium‐Ion Batteries

Control and Optimization of the Electrochemical and Mechanical Properties of the Solid Electrolyte Interphase on Silicon Electrodes in Lithium Ion Batteries

Electrochemical Scanning Probe Microscopies in Electrocatalysis

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